Arylated aminonaphthalene derivatives



Patented May 10, 1932 warren STATES PATENT OFFICE HEINRICH HEIMANN AND PAUL vIRcK, 0F DESSAU IN ANHALT, GERMANY, Assienons r T0 GENERAL ANILINE WORKS, me, or new 201m, 1x1. 1., A conronA'rronon DELAWARE 1 No Drawing. Application filed November 28, 1927, Serial No. 236,358, and in German December 13, 1926.

In German Letters Patent Nos. 122,570, 125,589 and Zeitschrift fiir Farbenund Textil Chemie 1904, page 57 et seq. has been described the production of arylated aminonaphth'alene derivatives by treating aminonaphthalenes or hydroxynaphthalenes with primary amino-aryl-compounds of the ben- 'Chemie 1904, page 58, and-Journal fiir praktische Chemie II, 7 5, page 252).

In contradiction to these statements we have found that arylated compounds of aminonaphthalenes may be obtained corresponding to the general formula 1() 5 8-m B J-n n) m,

wherein Y stands for H or any univale t substituent except the groups -COOH, SO H and wherein at, least one X means the group --OR or I r (R, R, R see above) m and a meaning 1 or 2, by heating 1n the presence of an aqueous solution of a bisulfite salt a naphthalene com 7 pound of the general formula in which at least one Y represents the group ARYLATED AMINONAPHTHALENE DERIVATIVES +011 or un, and the H, halogen, +011,

pound of the general formula wherein n means 1. 2 or 3 and wherein at least ,1 i

I R", (R, R, R see above) and the other Xsmean H or a univalent substituent. The yields are very satisfactory and the products arein a other Ys represent 7 pure state if the reactiouis carried out under suitable conditions, namely whilst stirring intensivelyand at temperatures not considerably below theboiling point ofthe mixture to not considerably above 150 C. -When carrying out the reaction above the boiling point of the reaction mixture a closed vessel must be used; in this case the resulting pressure is a function from the temperature applied and from the tension of the reacting liquid. The treating of the reaction mixture at the temperatures given above is continued until a test prooves that unchanged naphthalene compound applied as starting material is no longer present. It is further of an ad-' vantage for obtaining a good yield that the amino benzene compound is used in an excess above the theoretical amount. When using 120-150 .per cent. of the theoretical amount of the amino benzene compound the best result is obtained, f I

The following examples serve to illustrate the invention:

(1) 144 parts of 2-hydroxynaphthalene and 150 parts of 1.2-diaminobenzene are stirred for 40 hours at a temperature of 115120 C. in a closed enameled vessel with 4000 parts of a solution of sodium bisulfite of 19 B. strength. After cooling to -70 C. the product of the reaction is separated from the aqueous solution and purified by dissolving in hot water which contains hydrochloric acid; After cooling the (2-aminophenyl) -2- aminonaphthalene-hydrochloride is separatbrown shades are obtained by a treatment with an oxidizing agent.

added.

(2) 144 parts of Q-hydrOXynaphthalene and 130 parts 1.8-dia1ninoben2ene-are heated to the boiling point for hours, whilst stirring, with 4000 parts of a solution of sodium bisule fite of 19 Be. strength in a leaded or enamelled vessel provided with a stirrer and a refiuX apparatus. The product of reaction separated from the hot aqueous solution; it may be purified by treating with hot water to which some sodium hydroxide solution is It may be recrystallized from a dilute solution of hydrochloric acid.

(3) 137 parts of 1.4-diaminobenzene and 144 parts of Q-hydroxynaphthalene are boiled for 100 hours, whilst stirring, with 4000 parts of a solution of sodium bisulfite of 20 B. strength in a leaded or enamelled vessel provided with a stirrer, a heating device and a reflux apparatus. After cooling to 60-70 C. the (4-aminophenyl) -2-aminonaphthalene thus obtained is filtered, pressed and well washed with warm Water. 1

When treating the l-hydroxynaphthalene under the same conditions the (4-aminophenyl) -1-aminonaphthalene is obtained.

(4) In a lead or enamelled vessel provided with a stirrer and a reflux apparatus 288 parts of 1amin0naphthalene, 400 parts of 4-a1ninc-4-hydroxydiphenylamine and 7000 parts of a solution of sodium bisulfite of about 20 B. strength are boiled whilst stirring until after about hours only small quantities of the unchanged starting materials are present. After cooling to 7 080 C. the product of reaction is separated by filtration. pressed and digested with a very dilute solution of hydrochloric acid and then with hot Water to remove the unchanged starting materials.

(5) In a vessel described in Example 3 parts of Q-hydrOXynaphthalene and 280 parts of 4.4 Q diaminodiphenylamine 2 sulfonic acid are boiled with-2000 partsof a solution of sodiumbisulfite of 36 B. strengthand 2000 parts of water for 5070 hours whilst stirring.

V The product of condensation is separated by addition of an organic acid. It is a sulfonic acid of 2-naphthylamino- (4f-aminodiphenylamine) of the formula which is purified by dissolving in a dilute so lution of sodium carbonate and reseparating 3 by addition of an acid; In an aqueous suspension containing soap it is absorbed by acetate silk which is dyed in blue shades by a subsequent treatment with a weal: oxidizing agent.

A corresponding derivative of 1amino naphthalene is obtained when applying 1- aminoor i-hydroxynaphthalene instead of 2hydroxynaphthalene.

(6) 144 parts of Q-hydroxynaphthalene and partsof 3-amino l-hydroxybenzene are stirred in a closed enamelled vessel provided with a stirring device with 4000 parts of a solution of sodium bisulfite of 20 B. strength for 30 hours at a temperature of 115120 C. After cooling to'6070 C. the, 5

product of reaction is separated from the solution and purified by boiling repeatedly with water.

(7) 143, parts of l-aininonathalene and l60jparts of l-amino-4-hydroxybenzene are stirred at a temperature of 112-115 C. for 4.0 hours with 4000 parts of a solution of sodium bisulfite of about 20l3. strength in, a closed enamelled vessel provided with a stirring device. After cooling to 60 C. the (.4-

pa ts of sodium bisulfite in 6000 p f water are'lieated for 12 hours to a temperature of 140145 C. After cooling to 70 C. the (4-hydr'oxyphenyl) -2-aniinonaphthalene thus" obtained is filtered and pressed and washed with hot water. It forms silver-gray needles. 7 Instead of. 2-hydroxynaphthalene the corresponding" quantity of Q-aminonaphthalene may be used.

(9) Parts Of hydroxynaphthalene are heated whilst stirring with parts of 4-amino 1 hydroxy 2 methylbenzene and 6000 parts of solution of sodium'bisulfite of 20 B. strength at a temperature of 130-185 C. for about 8 hours in an enamelled closed :33

vessel provided with a heating device and With a stirrer. After cooling to 80 C. the product of reaction is filtered, pressed and well washed with hot water. The (4-hydroxy- 3 -methylphenyl) -2- aminonaphthalene forms in the raw-state silver-gray leaflets. Recrystallized' from benzene and ligroin it has the melting point at 127-128 C.

It is easily soluble in alcohol, benzene and H ether.

are heated whilst stirring for 10 hours at a temperature of 125-130 C. with 5600 parts of a solution of sodium bisulfite of 15 Be. strength'and 240 parts of the sodium salt of (10) 144 parts of 2-a1nino-naphthalene a amino 1 hydroxybenzene 2 ca-rboxylici rer and a reflux apparatus. After cooling to about C. the 2.7-di(para-hydroxyphenylamino) -naphtha lene is separated in form of light-gray crystals, it is filtered, pressed and washed with hot water. The dried product obtainedin good yield has the melt ing point at 249-25? C.

(12) 160 parts of 1.5-dihydroxynaphthalene, 260 parts of 4-a-mino-1-hydroxybenzene,

400 parts of alkali metal bisulfite and 3000 parts of water are heated for 36 hours to a temperature of 115120 C.in a leaded closed vessel provided with a stirring device. After cooling the separated 1.5-di (para-hydroxyphenylamino) -naphthalene, forming fine needles, is pressed and washed with hot water& The dried compound melts at 278- 280 r A (13) 160 parts of 2.6-dihydroxynaphthalene and 260 parts of 4-hydroxy-1-aminobenzene are boiled with a solution of 400 parts of alkali-metal bisulfite in 3000 parts of water for 120 hours whilst stirring in an enamelled vessel provided with a stirring device and a reflux apparatus. After cooling to about C. the product ofreaction is filtered ofi, pressed and washed with hot water. It is recrystallized from dilutealcohol. The 2.6-

di(4 hydroxyphenylamino) naphthalene forms a greenish gray powder melting at 274278 C. In a similar way other dihydroxy-, diamino or aminohydroxynaphthalene-derivatives may be employed.

(14) parts of IA diaminObenZene and 100 parts of 2.7-dihydroxynaphthalene are boiled in an enamelled vessel providedwith a stirrer and a reflux apparatus with a solution of 400 parts of alkali metal bisulfite and f After cooling to 7 080 C. the product of reaction 3000 parts of water for'40 hours;

is filtered ofl". pressed and washed with hot water. The Q-(at-amiriophenylamino) -7-hydroxynaphthalene is purified from small quantities of by-products by dissolving in a dilute warm solution of sodium hydroxide and by precipitating from this solution with hydrochloric acid. This process of purificationmay be repeated. From a solution containing hydrochloric acid the 2(4:-.aminophenylamino) 7-hydroxynaphthalenehydro chloride isseparated by addition of common salt. In the dry state it forms a bluish gray powder which dissolves in water made weak ly acid by addition of hydrochloric acid. From this solution it is absorbed by animal fibers; by a subsequent treatment with an oxidizing agent these fibers are dyed in fast blue tints.

I It is obvious to those skilled in the art that our present invention is not limited to the foregoing examples or to the details given therein. naphthalenes chosenin the examples may be substituted by the corresponding aminonaphthalenes and vice versa. Furthermore Thus, for instance, the hydroxyother aminobenzen'e-derivatives substituted 5 in the manner mentioned above may be employed. It may be stated that instead .of'so dium bisulfite other soluble bisulfite salts may be used. It is advantageouswhen employing a more dilute solution of solublebisulfitesalt to heat to a higher'temperature, and when w employing a more concentrated solution to heat only nearly to the boiling point ofthe I pound employed in an excess mayberecovered and re-used.

What we claim is:

1. The process which comprises treating reactionmixture. The aminobenzene'coma naphthalene compound of the generalforg mula V I 1-oH7 I in which'Zrepre'sentst-he group 011x51 NH with 1-ami-no--hydroxybenzene, while agitating, in thep'resence of an aqueous solution of abisulfitesalt at a temperature, between about 100 C. and about 145 C. 2. The process which comprises treating. a naphthalene compoundof the generalfor mula q 1 V in which Z representsthe giroup-OH or -NH with 1.-amino--hydroxybenzene, while agitating,'in the presenceof an aqueous solution of abisulfitesalt at a temperature between about 100 C. and about145 C.

3. The process which comprises treating a naphthalene compound ofthe general formula - general formula tating in the presence of an aqueous solution of a bisulfite salt at a temperature between about 100 C. and about 145 C. a

4. The process which comprises treating anaphthalene compound of the general formula in which Z represents the group OH or NH with an amino compound of the wherein n meansl or 2, and wherein one/X means OH and the other X may be H, methyl, or a carboxylic acid group, while agitating in the presence of an aqueous solution 7 of a bisulfite salt at a temperature between about 100 C. and about 145 C.

5. The process which comprises treating a naphthalene.compound of the general formula (n in which Z represents the group -OH or -NH with an amino compound of the general formula H2N-O H 5 X wherein n means 1 or 2, and wherein one X means OH and the other X may be H,

' methyl, or a carboXylic acid group, while agitating in the presence of an aqueous solution of a bisulfite salt at a temperature between about 100 C. and about 145 C.

6. The process which comprises treating a naphthalene compound of the general forin which Z represents the group -OH or NH with an amino compound of the general formula while agitating in the presence of an aqueous solution of a bisulfitesalt at a temperature between about 100 C; and about 145 C.

7. The process which comprises treating a naphthalene compound of the general'formula 1 in which Z represents the group OH or NH with an amino compound of the general formula while agitating in the presence of an aqueous solution of a bisulfite salt at a temperature between about 100 C. and about 145 C.

8. The process which comprises treating Q-hydroxynaphthalene with 1-amino-4-hy- I 2-hydroxynaphthalene with 4-amino-11-hydroxy-Q-methylbenzene, while agitating, in

the presence of anaqueous solution ofv a bisulfite salt at a temperature betweenabout C. and about C. V V 1 In testimony whereof, we alfix our signatures.

I PAUL VI RCK.

" HEINRICH HEIMANN." 7 

